US4092148A - Amide derivatives of 1,3,4-thiadiazoles - Google Patents

Amide derivatives of 1,3,4-thiadiazoles Download PDF

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US4092148A
US4092148A US05/012,135 US1213570A US4092148A US 4092148 A US4092148 A US 4092148A US 1213570 A US1213570 A US 1213570A US 4092148 A US4092148 A US 4092148A
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hydrogen
trifluoromethyl
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composition
chlorodifluoromethyl
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Tony Cebalo
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Air Products and Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C07D285/135—Nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • the present invention relates to thiadiazoles and, more particularly to amide derivatives of 1,3,4-thiadiazoles having a halogenated alkyl group in the 5-position. It is known in the art that various types of thiadiazole compositions may be used for pesticidal purposes. For example, Belgian Pat. No. 721,034 teaches that certain compounds, only generally related to that taught in the present invention, have herbicidal properties. However, the particular compounds of the present invention are believed to have biological activity which has heretobefore not known nor anticipated.
  • amide derivatives of 1,3,4-thiadiazoles having the general structure: ##STR2## wherein R 1 is a halogenated C 1 to C 4 acyclic hydrocarbon radical, wherein the halogen is fluorine, chlorine and/or bromine
  • R 2 is hydrogen or a C 1 to C 4 acyclic hydrocarbon radical
  • R 3 is hydrogen, a C 1 to C 4 acyclic hydrocarbon radical, a halogenated C 1 to C 4 acyclic hydrocarbon radical or cycloalkyl.
  • R 1 , R 2 and R 3 will have the same definition throughout the specification and claims.
  • the compounds show highly desirable activity as agricultural pesticides, particularly as herbicides, for controlling a broad spectrum of unwanted and undesirable weeds and plants.
  • the compounds (I) of the invention may be prepared by methods generally known in the art. For example, the following reactions may be employed:
  • R 1 is a halogenated lower alkyl radical containing from 1 to 4 carbon atoms, the halogen being selected from fluorine, chlorine, bromine, preferably fluorine;
  • R 2 is a lower alkyl radical containing from 1 to 4 carbon atoms and R 3 is hydrogen, a lower alkyl radical containing 1 to 4 carbon atoms; a halogenated lower alkyl radical, the halogen being fluorine, chlorine or bromine or a cycloalkyl radical having from 1 to 4 carbon atoms.
  • a mixture containing 5.07 gms of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole, 9.68 gms of chlorodifluoroacetic anhydride and 5 mls of chlorodifluoroacetic acid were heated at a about 100° C for 1 hour and heated an additional 1 hour at about 120° C.
  • the reaction mixture was subsequently poured into benzene, mixed thoroughly and the benzene decanted from the insoluble material.
  • the benzene solution was concentrated under vacuum to give a solid which was recrystallized from in a benzene/n-hexane mixture.
  • the resulting product was identified to be N-(5-trifluoromethyl-1,3,4-thiadiazole) chlorodifluoroacetamide and having a melting point of 150° - 152° C.
  • the resulting solid material was separated by filtering and subsequently recrystallized from benzene to provide a product identified to be N-(5-trifluoromethyl)-1,3,4-thiadiazol-2-yl) dichloroacetamide having a melting point of 173.5° - 174.5° C.
  • the compounds of the invention have utility as herbicides. Some of them may be applied to soil for use as pre- and post-emergence herbicides. Others may be used in various states of purity ranging, for example, from purified crystals to a technical crude grade. Suitable solvents for these compounds include alcohols, aqueous alcohol and ketone solutions, including acetone, and related ketones such as methyl isobutyl ketone.
  • the test procedure involved preparation of the indicated compounds as 50% wettable powders which were extended in water to obtain final spray suspensions.
  • the active ingredient was applied at the rates (i.e. expressed as pounds of active compound per acre) indicated in the Table.
  • Tests were made on pigweed, setaria, Johnson Grass, morning glory, tomatoes, oats, wheat, cucumbers, red kidney beans (RKB), and cotton. Generally these plants were two weeks of age at the time of application. In the case of cotton, it was in its four to six leaf stage at the time of spray application.
  • the red kidney beans, when sprayed, were at a point in their growth where they had a well expanded set of first true leaves.
  • Table 3 shows additional herbicidal activity of the compounds of the invention.
  • the first numbers in the ratio indicate the phytotoxicity rating from 0 to 10 as previously described.
  • the second number or letter indication is whether or not there was evidence of Necroses (Ne), Retardation of growth (R), or no effect at all (0), e.g. 9:Ne.
  • compounds of the invention When utilized for herbicidal purposes, compounds of the invention may be formulated in a variety of ways and concentrations for application to the locus of desired vegetation control. It is recognized that the particular type and concentration of formulation, as well as the mode of application of the active ingredient, may govern its biological activity in a given application.
  • Compounds of the invention may be prepared as simple solutions of the active ingredient in an appropriate solvent in which it is completely soluble at the desired concentration.
  • solvent systems include water, alcohols, acetone, aqueous alcohol and acetone and other organic solvents.
  • These simple solutions may be further modified by the addition of various surfactants, emulsifying or dispersing agents, colorants, odorants, antifoaming agents, other herbicides or herbicidal oils which supplement or synergize the activity of the herbicides of the invention, or other adjuvants for any given application where deemed desirable to impart a particular type or degree of plant responses.
  • compositions containing the active ingredient include, for example, compositions containing the active ingredient as granules of relatively large particle size, as powder dusts, as wettable powders, as emulsifiable concentrates or as a constituent part of any other known type of formulation commonly utilized by those skilled in the art.
  • Such formulations include the adjuvants and carriers normally employed for facilitating the dispersion of active ingredient for agricultural and industrial applications of phytotoxicants. These formulations may contain as little as 0.25% or more than 95% by weight of the active ingredient.
  • Dust formulations are prepared by mixing the active ingredient with finely divided solids which act as dispersants and carriers for the phytotoxicant in applying it to the locus of application for vegetation control.
  • Typical solids which may be utilized in preparing dust formulations of the active ingredients of the invention include talc, kieselguhr, finely divided clay, fullers' earth, or other common organic or inorganic solids.
  • Solids utilized in preparing dust formulations of the active ingredient normally have a particle size of 50 microns or less. The active ingredient of these dust formulations is present commonly from as little as 0.25% to as much as 30% or more by weight of the composition.
  • Granular formulations of the active ingredients are prepared by impregnating or adsorbing the toxicant on or into relatively coarse particles of inert solids such as sand, attapulgite clay, gypsum, corn cobs or other inorganic or organic solids.
  • the active ingredient of these granular formulations is commonly present from 1.0% to as much as 20.0% or more by weight of the composition.
  • Wettable powder formulations are solid compositions of matter wherein the active ingredient is absorbed or adsorbed in or on a sorptive carrier such as finely divided clay, talc, gypsum, lime, wood flour, fullers' earth, kiesselguhr, or the like. These formulations preferably are made to contain 50% to 80% of active ingredient. These wettable powder formulations commonly contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion in water or other liquid carrier utilized to distribute the phytotoxicant to the locus of desired vegetation control.
  • a sorptive carrier such as finely divided clay, talc, gypsum, lime, wood flour, fullers' earth, kiesselguhr, or the like. These formulations preferably are made to contain 50% to 80% of active ingredient.
  • These wettable powder formulations commonly contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion in water or other liquid carrier utilized to distribute the phytotoxic
  • Emulsifiable concentrate formulations are homogeneous liquid or paste compositions containing the active ingredient which will disperse in water or other liquid carrier to facilitate application of the phytotoxicant to the locus of desired vegetation control.
  • Such emulsifiable concentrate formulations of the active ingredients may contain only the active ingredient with a liquid or solid emulsifying agent or may contain other relatively nonvolatile organic solvents such as isophorones, dioxane, heavy aromatic naphthas, xylene, or dimethyl formamide.
  • the active ingredient in such formulations commonly comprises 10.0% to 70.0% by weight of the phytotoxicant composition.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Novel thiadiazole compounds are taught and disclosed having the following general structure: ##STR1## wherein R1 is a halogenated C1 to C4 acyclic hydrocarbon radical, wherein the halogen is fluorine, chlorine and/or bromine,
R2 is hydrogen or a C1 to C4 acyclic hydrocarbon radical, and
R3 is hydrogen, a C1 to C4 acyclic hydrocarbon radical, a halogenated C1 to C4 acyclic hydrocarbon radical or cycloalkyl.
The compounds show particular utility as agricultural pesticides and, most favorably, as herbicides.

Description

BACKGROUND OF THE INVENTION
The present invention relates to thiadiazoles and, more particularly to amide derivatives of 1,3,4-thiadiazoles having a halogenated alkyl group in the 5-position. It is known in the art that various types of thiadiazole compositions may be used for pesticidal purposes. For example, Belgian Pat. No. 721,034 teaches that certain compounds, only generally related to that taught in the present invention, have herbicidal properties. However, the particular compounds of the present invention are believed to have biological activity which has heretobefore not known nor anticipated.
SUMMARY OF THE INVENTION
In accordance with the present invention, certain amide derivatives of 1,3,4-thiadiazoles are provided having the general structure: ##STR2## wherein R1 is a halogenated C1 to C4 acyclic hydrocarbon radical, wherein the halogen is fluorine, chlorine and/or bromine
R2 is hydrogen or a C1 to C4 acyclic hydrocarbon radical, and
R3 is hydrogen, a C1 to C4 acyclic hydrocarbon radical, a halogenated C1 to C4 acyclic hydrocarbon radical or cycloalkyl.
The particular designation of R1, R2 and R3 will have the same definition throughout the specification and claims.
The compounds show highly desirable activity as agricultural pesticides, particularly as herbicides, for controlling a broad spectrum of unwanted and undesirable weeds and plants.
PREFERRED EMBODIMENTS OF THE INVENTION
The compounds (I) of the invention may be prepared by methods generally known in the art. For example, the following reactions may be employed:
1. The reaction of primary or secondary amines with acid anhydrides, e.g. ##STR3## 2. The reaction of primary or secondary amines with an acid, e.g. ##STR4## 3. The reaction of primary or secondary amines with acyl halides, with or without an acid acceptor such as tertiary amines, pyridine, sodium carbonate, etc., e.g. ##STR5## where X = F, Cl or Br
In the compounds of the present invention, it is preferred that R1 is a halogenated lower alkyl radical containing from 1 to 4 carbon atoms, the halogen being selected from fluorine, chlorine, bromine, preferably fluorine; R2 is a lower alkyl radical containing from 1 to 4 carbon atoms and R3 is hydrogen, a lower alkyl radical containing 1 to 4 carbon atoms; a halogenated lower alkyl radical, the halogen being fluorine, chlorine or bromine or a cycloalkyl radical having from 1 to 4 carbon atoms.
The following examples are illustrative of the invention and are not intended to limit the scope thereof.
EXAMPLE 1
Six grams of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole were dissolved in 20 mls of trifluoroacetic anhydride and refluxed for about 2 hours and subsequently concentrated under vacuum. The residue weighing 9.1 gms was recrystallized from ethyl acetate/n-hexane to provide a product identified to be N-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl) trifluoroacetamide having a melting point of 168° - 170° C.
______________________________________                                    
                  C     H        N                                        
______________________________________                                    
C.sub.5 HF.sub.6 N.sub.3 OS                                               
            Required, % 22.66   0.38  15.86                               
            Found, %    22.75   0.42  15.74                               
______________________________________
EXAMPLE 2
A mixture containing 5.07 gms of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole, 9.68 gms of chlorodifluoroacetic anhydride and 5 mls of chlorodifluoroacetic acid were heated at a about 100° C for 1 hour and heated an additional 1 hour at about 120° C. The reaction mixture was subsequently poured into benzene, mixed thoroughly and the benzene decanted from the insoluble material. The benzene solution was concentrated under vacuum to give a solid which was recrystallized from in a benzene/n-hexane mixture. The resulting product was identified to be N-(5-trifluoromethyl-1,3,4-thiadiazole) chlorodifluoroacetamide and having a melting point of 150° - 152° C.
______________________________________                                    
                   N     S       Cl                                       
______________________________________                                    
C.sub.5 HC1F.sub.5 N.sub.3 OS                                             
             Required, % 14.93   11.39 12.60                              
             Found, %    15.10   11.76 12.28                              
______________________________________
EXAMPLE 3
To a stirred suspension containing 4.2 gms of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole and 2 gms of pyridine in benzene cooled at 10° C was added dropwise 4 gms of dichloroacetyl chloride. After complete addition of the dichloroacetyl chloride, the reaction mixture was refluxed for 2 hours, filtered while hot and the filtrate cooled to 5° C. The resulting solid material was separated by filtering and subsequently recrystallized from benzene to provide a product identified to be N-(5-trifluoromethyl)-1,3,4-thiadiazol-2-yl) dichloroacetamide having a melting point of 173.5° - 174.5° C.
______________________________________                                    
C.sub.5 H.sub.2 O.sub.2 F.sub.3 N.sub.3 OS                                
             Required, % 21.45   0.72  15.01                              
             Found, %    21.43   0.74  15.19                              
______________________________________
EXAMPLE 4
To a stirred suspension containing 4.2 gms of 2-amino-5-trifluoromethyl-1,3,4-thiadiazol in benzene which was cooled to 10° C was added, dropwise, 4.5 gms of trichloroacetyl chloride. After complete addition of the latter, the reaction mixture was refluxed for 2 hours and subsequently concentrated under vacuum. The resulting solid residue was recrystallized from benzene to provide a product identified to be N-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)trichloroacetamide having a melting point of 121° - 122° C.
______________________________________                                    
                   C     H       N                                        
______________________________________                                    
C.sub.5 HCl.sub.3 F.sub.3 N.sub.3 OS                                      
             Required, % 19.06   0.32  13.34                              
             Found, %    18.70   0.32  12.90                              
______________________________________
EXAMPLE 5
A mixture containing 10 gms of 2-amino-5-trifluoromethyl-1,3,4-thiadiazol-and 6.7 gms of isobutyryl chloride was refluxed in benzene for 2 hours. The reaction mixture was cooled to 5° C, the solid material separated by filtering and recrystallized from aqueous methanol to provide a product identified to be N-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)isobutyramide having a melting point of 145° - 146° C.
______________________________________                                    
                  C     H       N                                         
______________________________________                                    
C.sub.7 H.sub.8 F.sub.3 N.sub.3 OS                                        
            Required, % 35.18   3.37  17.58                               
            Found, %    34.68   3.30  17.78                               
______________________________________
EXAMPLE 6
A mixture containing 5.07 gms of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole and 3.45 gms of cyclopropane carboxylic chloride was stirred and refluxed for 3 hours in 100 mls of benzene. The reaction mixture was filtered and the filtrate concentrated under vacuum to a solid which was subsequently recrystallized from benzene to provide a product identified to be N-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)cyclopropane carboxamide having a melting point of 205° - 206° C.
______________________________________                                    
                  C     H       N                                         
______________________________________                                    
C.sub.7 H.sub.6 F.sub.3 N.sub.3 OS                                        
            Required, % 35.47   2.55  17.71                               
            Found, %    35.36   2.47  17.46                               
______________________________________
EXAMPLE 7
A mixture containing 2.3 gms of 2-amino-5-pentafluoroethyl-1,3,4-thiadiazole and 1.3 gms of isobutyryl chloride in benzene was refluxed for about 3 hours. The reaction mixture was concentrated under vacuum and the resulting solid recrystallized from aqueous methanol to provide a product identified to be N-(pentafluoroethyl-1,3,4-thiadiazol-2-yl)isobutyramide having a melting point of 95° - 97° C.
EXAMPLE 8
A mixture containing 2 gms of 2-amino-5-chlorodifluoromethyl-1,3,4-thiadiazole and 2.1 gms of trichloroacetyl chloride in 50 mls of benzene was refluxed for about 6 hours. The reaction mixture was concentrated under vacuum and the resulting solid recrystallized from aqueous methanol to provide a product identified to be N-(5-chlorodifluoromethyl-1,3,4-thiadiazol-2-yl)trichloroacetamide having a melting point of 116° - 119° C.
______________________________________                                    
                   C     H       N                                        
______________________________________                                    
C.sub.5 HCl.sub.4 F.sub.2 N.sub.3 OS                                      
             Required, % 17.61   0.30  12.32                              
             Found, %    17.54   0.90  12.34                              
______________________________________
EXAMPLE 9
A mixture containing 8 gms of 2-methylamino-5-trifluoromethyl-1,3,4-thiadiazole and 4.7 gms of trichloroacetyl chloride in benzene was refluxed for about 4 hours. The resulting solution was concentrated under vacuum to provide an oil product identified to be N-methyl-N-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)trichloroacetamide.
______________________________________                                    
                   C     H       N                                        
______________________________________                                    
C.sub.6 H.sub.3 Cl.sub.3 F.sub.3 N.sub.3 OS                               
             Required, % 21.97   0.92  12.81                              
             Found, %    22.16   1.21  12.99                              
______________________________________
Other examples for the preparation of representative compounds of the invention, as produced in accordance with the above methods hereinbefore described, are presented in Table I below.
              TABLE I                                                     
______________________________________                                    
Compounds corresponding to the general structure:                         
 ##STR6##                                                                 
Example No. R.sub.1       R.sub.2 R.sub.3                                 
______________________________________                                    
10          CF.sub.3    H         H                                       
11          CClF.sub.2  H         CH(CH.sub.3).sub.2                      
12          CH.sub.2 CH.sub.2 CH.sub.2 Br                                 
                        H         CCl.sub.3                               
13          CHF.sub.2   H         CF.sub.2 Cl                             
______________________________________
As stated above, the compounds of the invention have utility as herbicides. Some of them may be applied to soil for use as pre- and post-emergence herbicides. Others may be used in various states of purity ranging, for example, from purified crystals to a technical crude grade. Suitable solvents for these compounds include alcohols, aqueous alcohol and ketone solutions, including acetone, and related ketones such as methyl isobutyl ketone.
POST EMERGENCE HERBICIDAL ACTIVITY
Compounds of the invention were tested for post-emergence herbicidal activity. Presented below are some nonlimiting illustrations for their use in this connection.
The test procedure involved preparation of the indicated compounds as 50% wettable powders which were extended in water to obtain final spray suspensions. The active ingredient was applied at the rates (i.e. expressed as pounds of active compound per acre) indicated in the Table. Tests were made on pigweed, setaria, Johnson Grass, morning glory, tomatoes, oats, wheat, cucumbers, red kidney beans (RKB), and cotton. Generally these plants were two weeks of age at the time of application. In the case of cotton, it was in its four to six leaf stage at the time of spray application. The red kidney beans, when sprayed, were at a point in their growth where they had a well expanded set of first true leaves.
At 10 to 12 days after the spray application the results were observed. Phytotoxicity ratings were assigned based upon a scale from 0 to 10 in which 0 indicates no injuries and the number 10 indicates that all plants were killed. Representative data are presented in Table 2. In addition to the numbers, the following symbols are used to indicate the total observation made:
Des -- Desiccation
Y -- yellowing
X -- 50% desiccation
Table 3 shows additional herbicidal activity of the compounds of the invention. The first numbers in the ratio indicate the phytotoxicity rating from 0 to 10 as previously described. The second number or letter indication is whether or not there was evidence of Necroses (Ne), Retardation of growth (R), or no effect at all (0), e.g. 9:Ne.
                                  TABLE 2                                 
__________________________________________________________________________
POST EMERGENCE ACTIVITY                                                   
PRODUCT                                                                   
OF                                                     Red                
EXAMPLE                                                                   
       DOSE        Yellow                                                 
                        Johnsons                                          
                              Morning                  Kidney             
NO.    LBS/ACRE                                                           
              Pigweed                                                     
                   Foxtail                                                
                        Grass Glory Tomato                                
                                          Oats                            
                                             Wheat                        
                                                 Cucumber                 
                                                       Bean               
                                                           Cotton         
__________________________________________________________________________
2      2.5    9    10   4     10    10    6  6   10    6Y  6 Des          
       1.25   4    8    0     10    10    4  2    7    5   5              
       0.625  2    7    0     10    10    0  0    2    5   0              
3      2.5    6    9    6     10     8    9  7   10    10  7              
       1.25   4    9    3      9     7    5  5    9    7   5              
       0.625  2    7    2      7     5    0  0    7    5   3              
4      2.5    7    8    4     10    9Y    6   6Y 10    7   4Y             
       1.25   4    6    2     10    8Y    3  4   10    5   3Y             
       0.625  3    4    0      9    7Y    0  0    9    2   2Y             
5      2      5    10   8     10     8    9  5   10    7                  
                                                           5Xs            
       1      3    7    5     10     2    4  1   10    7                  
                                                           3Xs            
       0.5    1    5    2      8     0    1  0   10    6                  
                                                           2 s            
__________________________________________________________________________

                                  TABLE 3                                 
__________________________________________________________________________
PHYTOTOXIC RATING                                                         
PRODUCT                                                                   
OF                                            Barn                        
EXAMPLE                                                                   
       DOSE   Sugar                       Yellow                          
                                              yard                        
                                                  Crab                    
                                                      Buck-               
                                                          Morning         
NO.    LBS/ACRE                                                           
              Beets                                                       
                  Corn                                                    
                     Oats                                                 
                        Clover                                            
                            Soybean                                       
                                 Cotton                                   
                                     Mustard                              
                                          Foxtail                         
                                              Grass                       
                                                  Grass                   
                                                      wheat               
                                                          Glory           
__________________________________________________________________________
10     2      0:0 0:0                                                     
                     0:0                                                  
                        8:Ne                                              
                            1:Ne 5:Ne                                     
                                     7:Ne 0:0 0:0 0:0 10:Ne               
                                                          2:Ne            
       1      0:0 0:0                                                     
                     0:0                                                  
                        4:Ne                                              
                            1:Ne 3:Ne                                     
                                     5:Ne 0:0 0:0 0:0 10:Ne               
                                                          1:Ne            
       0.5    0:0 0:0                                                     
                     0:0                                                  
                        0:0 1:Ne 0:0 2:Ne 0:0 0:0 0:0 10:Ne               
                                                          0:Ne            
11     2      9:Ne                                                        
                  0:0                                                     
                     0:0                                                  
                        10:Ne                                             
                            5:Ne 10:Ne                                    
                                     3:R  3:R 1:R 0:0 10:Ne               
                                                          0:0             
       1      8:Ne                                                        
                  0:0                                                     
                     0:0                                                  
                        9:Ne                                              
                            3:Ne 4:Ne                                     
                                     8:Ne 1:R 0:0 0:0 10:Ne               
                                                          0:0             
       0.5    7:Ne                                                        
                  0:0                                                     
                     0:0                                                  
                        8:Ne                                              
                            1:Ne 4:Ne                                     
                                     8:Ne 0:0 0:0 0:0 10:Ne               
                                                          0:0             
__________________________________________________________________________
When utilized for herbicidal purposes, compounds of the invention may be formulated in a variety of ways and concentrations for application to the locus of desired vegetation control. It is recognized that the particular type and concentration of formulation, as well as the mode of application of the active ingredient, may govern its biological activity in a given application.
Compounds of the invention may be prepared as simple solutions of the active ingredient in an appropriate solvent in which it is completely soluble at the desired concentration. Such solvent systems include water, alcohols, acetone, aqueous alcohol and acetone and other organic solvents. These simple solutions may be further modified by the addition of various surfactants, emulsifying or dispersing agents, colorants, odorants, antifoaming agents, other herbicides or herbicidal oils which supplement or synergize the activity of the herbicides of the invention, or other adjuvants for any given application where deemed desirable to impart a particular type or degree of plant responses.
Compounds of the invention may also be formulated in various types of formulations commonly recognized by those skilled in the art of agricultural or industrial chemicals. These formulations include, for example, compositions containing the active ingredient as granules of relatively large particle size, as powder dusts, as wettable powders, as emulsifiable concentrates or as a constituent part of any other known type of formulation commonly utilized by those skilled in the art. Such formulations include the adjuvants and carriers normally employed for facilitating the dispersion of active ingredient for agricultural and industrial applications of phytotoxicants. These formulations may contain as little as 0.25% or more than 95% by weight of the active ingredient.
Dust formulations are prepared by mixing the active ingredient with finely divided solids which act as dispersants and carriers for the phytotoxicant in applying it to the locus of application for vegetation control. Typical solids which may be utilized in preparing dust formulations of the active ingredients of the invention include talc, kieselguhr, finely divided clay, fullers' earth, or other common organic or inorganic solids. Solids utilized in preparing dust formulations of the active ingredient normally have a particle size of 50 microns or less. The active ingredient of these dust formulations is present commonly from as little as 0.25% to as much as 30% or more by weight of the composition.
Granular formulations of the active ingredients are prepared by impregnating or adsorbing the toxicant on or into relatively coarse particles of inert solids such as sand, attapulgite clay, gypsum, corn cobs or other inorganic or organic solids. The active ingredient of these granular formulations is commonly present from 1.0% to as much as 20.0% or more by weight of the composition.
Wettable powder formulations are solid compositions of matter wherein the active ingredient is absorbed or adsorbed in or on a sorptive carrier such as finely divided clay, talc, gypsum, lime, wood flour, fullers' earth, kiesselguhr, or the like. These formulations preferably are made to contain 50% to 80% of active ingredient. These wettable powder formulations commonly contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion in water or other liquid carrier utilized to distribute the phytotoxicant to the locus of desired vegetation control.
Emulsifiable concentrate formulations are homogeneous liquid or paste compositions containing the active ingredient which will disperse in water or other liquid carrier to facilitate application of the phytotoxicant to the locus of desired vegetation control. Such emulsifiable concentrate formulations of the active ingredients may contain only the active ingredient with a liquid or solid emulsifying agent or may contain other relatively nonvolatile organic solvents such as isophorones, dioxane, heavy aromatic naphthas, xylene, or dimethyl formamide. The active ingredient in such formulations commonly comprises 10.0% to 70.0% by weight of the phytotoxicant composition.
In place of the particular compounds used in the Examples, other compounds, as hereinbefore described and taught, may also be employed to provide substantially the same results.

Claims (24)

What is claimed is:
1. A herbicidal composition comprising a carrier and a herbicidal amount of at least one compound having the general formula: ##STR7## wherein R1 is trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl,
R2 is hydrogen or C1 -C4 alkyl, and
R3 is hydrogen, C1 -C4 alkyl, C1 -C4 haloalkyl or cyclopropyl, the halogen being fluorine, chlorine or bromine.
2. The composition of claim 1 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is trichloromethyl.
3. The composition of claim 1 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is chlorodifluoromethyl.
4. The composition of claim 1 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is dichloromethyl.
5. The composition of claim 1 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is isopropyl.
6. The composition of claim 1 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is cyclopropyl.
7. The composition of claim 1 wherein R1 is pentafluoroethyl, R2 is hydrogen and R3 is isopropyl.
8. The composition of claim 1 wherein R1 is chlorodifluoromethyl, R2 is hydrogen and R3 is trichloromethyl.
9. The composition of claim 1 wherein R1 is trifluoromethyl, R2 is methyl and R3 is trichloromethyl.
10. The composition of claim 1 wherein R1 is chlorodifluoromethyl, R2 is hydrogen and R3 is isopropyl.
11. The composition of claim 1 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is hydrogen.
12. A method for controlling plants which comprises applying to the locus to be treated, a herbicidal amount of at least one compound having the general formula: ##STR8## wherein, R1 is trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl,
R2 is hydrogen or C1 -C4 alkyl, and
R3 is hydrogen, C1 -C4 alkyl, C1 -C4 haloalkyl or cyclopropyl, the halogen being fluorine, chlorine or bromine.
13. The method of claim 12 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is trichloromethyl.
14. The method of claim 12 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is chlorodifluoromethyl.
15. The method of claim 12 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is dichloromethyl.
16. The method of claim 12 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is isopropyl.
17. The method of claim 12 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is cyclopropyl.
18. The method of claim 12 wherein R1 is pentafluoroethyl, R2 is hydrogen and R3 is isopropyl.
19. The method of claim 12 wherein R1 is chlorodifluoromethyl, R2 is hydrogen and R3 is trichloromethyl.
20. The method of claim 12 wherein R1 is trifluoromethyl, R2 is methyl and R3 is trichloromethyl.
21. The method of claim 12 wherein R1 is chlorodifluoromethyl, R2 is hydrogen and R3 is isopropyl.
22. The method of claim 12 wherein R1 is trifluoromethyl, R2 is hydrogen and R3 is hydrogen.
23. The composition of claim 1 wherein R1 is trifluoromethyl, R2 is butyl and R3 is trichloromethyl.
24. The method of claim 12 wherein R1 is trifluoromethyl, R2 is butyl and R3 is trichloromethyl.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4187098A (en) * 1978-11-24 1980-02-05 Gulf Oil Corporation Selectively herbicidal N-(5-substituted-2-thiadiazolyl)-thiocarboxamides
US4237302A (en) * 1978-09-29 1980-12-02 Gulf Oil Corporation Dichloroacetylimino herbicide antagonists as plant protection agents
US4264616A (en) * 1980-08-29 1981-04-28 Gulf Oil Corporation 2-Iodoacetylimino-3-methyl-5-trifluoromethyl-1,3,4-thiadiazol-4-ine and use as a fungicide
US4279636A (en) * 1978-09-29 1981-07-21 Gulf Oil Corporation Dichloroacetylimino herbicide antagonists as plant protection agents
US4337081A (en) * 1979-01-23 1982-06-29 Olin Corporation 5-Amido-3-trihalomethyl-1,2,4-thiadiazoles and their use as herbicides
US4382142A (en) * 1978-10-18 1983-05-03 Kowa Co., Ltd. Thiadiazole derivatives and process for preparing same

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BE736854A (en) 1968-08-01 1970-02-02
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237302A (en) * 1978-09-29 1980-12-02 Gulf Oil Corporation Dichloroacetylimino herbicide antagonists as plant protection agents
US4279636A (en) * 1978-09-29 1981-07-21 Gulf Oil Corporation Dichloroacetylimino herbicide antagonists as plant protection agents
US4382142A (en) * 1978-10-18 1983-05-03 Kowa Co., Ltd. Thiadiazole derivatives and process for preparing same
US4187098A (en) * 1978-11-24 1980-02-05 Gulf Oil Corporation Selectively herbicidal N-(5-substituted-2-thiadiazolyl)-thiocarboxamides
US4337081A (en) * 1979-01-23 1982-06-29 Olin Corporation 5-Amido-3-trihalomethyl-1,2,4-thiadiazoles and their use as herbicides
US4264616A (en) * 1980-08-29 1981-04-28 Gulf Oil Corporation 2-Iodoacetylimino-3-methyl-5-trifluoromethyl-1,3,4-thiadiazol-4-ine and use as a fungicide
EP0047052A1 (en) * 1980-08-29 1982-03-10 Gulf Oil Corporation 2-Iodoacetylimino-3-methyl-5-trifluoromethyl-1,3,4-thiadiazol-4-ine and use as a fungicide

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